2021
DOI: 10.1016/j.matt.2021.05.004
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Tandem photoelectrochemical and photoredox catalysis for efficient and selective aryl halides functionalization by solar energy

Abstract: Solar energy conversion is the most important chemical transformation for green and sustainable society. Represented herein is a coupled photoelectrochemical/ photoredox (c-PEC/PC) strategy for efficient, selective and challenging organic transformations by sunlight. Under visible and near-infrared light irradiation, the c-PEC/PC setting obtains high reducing ability at a low applied potential, which realizes reductive functionalization of aryl halides, including late-stage functionalization of pharmaceutical … Show more

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Cited by 34 publications
(15 citation statements)
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“…To overcome these limitations, recent innovations have provided catalytic methods allowing the input of additional energy beyond a single visible photon to generate extremely strong reducing agents (Figure A). , One appealing approach is capturing the energy from multiple photons within a single catalyst turnover. , In these “Z-scheme” reactions, initial photoexcitation and reductive quenching of the photocatalyst produce a reduced catalyst species, which can then absorb a second photon to form a powerfully reducing excited state. ,, While this strategy has unlocked new photocatalyzed reductive transformations, such procedures present their own challenges. The photocatalyst must absorb visible photons in the ground state and after conversion to the active photoreductant via reduction, while additionally having appropriate excited state properties to drive chemistry after each successive excitation. , In complement to this advance, others have pioneered electrochemical reduction of suitable precatalysts to form highly potent “electrochemically primed” photoredox catalysts. , By decoupling catalyst reduction from photoexcitation, this approach has greatly expanded the pool of competent reduction-activated photoreductants to include more accessible and durable catalysts and enabled new selective aryl radical chemistry by spatially separating the reaction mixture from potentially problematic reductants.…”
Section: Introductionmentioning
confidence: 99%
“…To overcome these limitations, recent innovations have provided catalytic methods allowing the input of additional energy beyond a single visible photon to generate extremely strong reducing agents (Figure A). , One appealing approach is capturing the energy from multiple photons within a single catalyst turnover. , In these “Z-scheme” reactions, initial photoexcitation and reductive quenching of the photocatalyst produce a reduced catalyst species, which can then absorb a second photon to form a powerfully reducing excited state. ,, While this strategy has unlocked new photocatalyzed reductive transformations, such procedures present their own challenges. The photocatalyst must absorb visible photons in the ground state and after conversion to the active photoreductant via reduction, while additionally having appropriate excited state properties to drive chemistry after each successive excitation. , In complement to this advance, others have pioneered electrochemical reduction of suitable precatalysts to form highly potent “electrochemically primed” photoredox catalysts. , By decoupling catalyst reduction from photoexcitation, this approach has greatly expanded the pool of competent reduction-activated photoreductants to include more accessible and durable catalysts and enabled new selective aryl radical chemistry by spatially separating the reaction mixture from potentially problematic reductants.…”
Section: Introductionmentioning
confidence: 99%
“…And moderate to excellent yields were obtained without formation of hydroarylation byproducts (3−20). Functionalities such as cyano (3 and 7−9), ester (4 5, 10, and 13−15), trifluoromethyl (12), phenyl ( 16), methoxy (42, Table S4), and methyl (43, Table S4) were well-tolerated. Notably, this paired electrolysis platform successfully enabled the C−F arylation of inert tetra- (9−11) and trifluoroarenes (3−8) and even a difluoroaromatic (20).…”
Section: ■ Results and Discussionmentioning
confidence: 99%
“…N , N -Bis­(2,6-diisopropylphenyl)­perylene-3,4,9,10-bis­(dicarboximide) (PDI) has a low reduction potential (( E 1/2 (PDI/PDI •– ) = −0.52 V vs SCE, Figure S7), and its photoexcited intermediate PDI •– * is highly reductive (−2.87 V vs SCE, Figure S8). , Considering that electrophotocatalysis integrates the power of electrochemistry and photochemistry, PDI •– * can be obtained through photoexcitation of PDI •– , which is generated by electroreduction of PDI. Herein, we postulate a transition-metal-free electrophotocatalytic reductive radical coupling approach (Figure B).…”
Section: Introductionmentioning
confidence: 99%
“…Although perylene diimide (PDI) structures were reported by Wickens to be inefficient for reductive aryl halide couplings, Wu subsequently developed an electrophotocatalytic reductive aryl halide functionalization method using PDI as the electrophotocatalyst (Figure 22A). 70 Notably, this system made use of a photocathode [Sb 2 (S, Se) 3 ] with a platinum anode under irradiation from a 500 W Xe lamp to achieve the reductive functionalization of aryl halides. This protocol thus utilized light in two different ways to promote these reactions.…”
Section: Reductive Electrophotocatalysismentioning
confidence: 99%